WO1997016525A1

WO1997016525A1 - Detergent grains and granular detergent composition

Info

Publication number: WO1997016525A1
Application number: PCT/JP1996/003209
Authority: WO
Inventors: Katsuhiko Kasai; Shu Yamaguchi; Hitoshi Takaya; Taiji Nakamae; Itsuro Tsukahara
Original assignee: Kao Corporation
Priority date: 1995-11-02
Filing date: 1996-10-31
Publication date: 1997-05-09
Also published as: EP0903404A4; US6335313B1; CN1200760A; CN1105177C; JPH09125098A; EP0903404A1; JP3008166B2; TW347413B

Abstract

Detergent grains containing at least 10 % by weight of a nonionic surfactant and at least 1 % by weight of a crystalline alkali metal silicate having an average particle diameter of from 1 to 60 νm, wherein the ratio by weight of the surfactant to the alkali metal silicate is from 20/1 to 1/20 and the alkali metal silicate is contaminated with iron in an amount of 140 ppm or less in terms of Fe; and a granular detergent composition containing these detergent grains.

Description

Detergent Damage Detergent particles and granular detergent composition t ^ fil

The present invention relates to a detergent particle and a granular detergent composition having good whiteness. More specifically, it contains a nonionic surfactant and a crystalline alkali metal silicate, and has good whiteness. The present invention relates to a detergent particle having the following and a granular detergent composition containing the same. Background art

In the detergent, in order to improve the cleaning performance, in addition to the surfactant, a builder that captures components that increase the hardness (such as Ca ²⁺ , Mg ²⁺ ) in tap water, and washing water A builder for maintaining the strength of the steel is included. Since eutrophication of rivers and lakes has become a social problem, zeolite has been increasingly used instead of phosphorus compounds (tripolyphosphate, etc.) as a builder to capture components that increase hardness. Alkaline builders usually use carbonates and amorphous gayates.

In recent years, crystalline alkali metal silicates, which have both a function of capturing hardness-increasing components and an alkaline buffering function that exhibits alkaline and buffering capabilities, have become known as detergent builders. (Japanese Patent Publication No. 1-411116). The crystalline alkali metal gaylate is not only a multifunctional builder having both alkaline and cation exchange capabilities, but also has the property of gradually dissolving after being released into the natural environment. are doing. Because of these characteristics, it is relatively environmentally friendly It has attracted attention as an excellent builder with a small load, and it has been found that a composition excellent in cleaning of fatty acid stains can be obtained especially when used in combination with a nonionic surfactant (Japanese Patent Application Laid-Open No. 6-10 / 1998). (Japanese Patent Application Laid-Open No. 2000, JP-A-6-116600).

Although such crystalline alkali metal gaylate is water-soluble, it only partially dissolves in a short period of time, such as washing time, and has a problem that it adheres to and remains on clothing as particles. In order to solve this problem, it is preferable to mix powder having an average particle diameter of several tens of meters or less.

Despite the fact that the crystalline alkali metal silicate powder obtained by pulverization is white, if it is blended in the same particles with a nonionic surfactant, the resulting detergent particles will appear gray. Was inevitable. This tendency was more remarkable in powdering such as pulverization and milling at an industrial level that required a large amount of powdering treatment in a short time. It has been known that a nonionic surfactant and a zeolite, an oil-absorbing carrier, a carbonate, and the like are blended in the same particle (Japanese Patent Application Laid-Open Nos. Hei 4-339988 and Hei 5-59). -5100 publication), the detergent particles of such a blend system are of a good white color, and the graying phenomenon of the detergent particles described above is due to the fact that the crystalline alkali metal gaylate and the non-ionic This phenomenon is peculiar to the case where the same surfactant is used in combination with the same particles.

In general, it goes without saying that a white powder is preferred for use as a detergent, and that a detergent containing a crystalline alkali metal silicate and a nonionic surfactant in the same particle has a high cleaning effect. Despite the performance, the gray hue resulted in a significant decrease in commercial value. Accordingly, an object of the present invention is to provide detergent particles of high commercial value having improved hue and good whiteness, and granular detergent compositions containing the same.

These and other objects of the present invention will become apparent from the following description. Disclosure of the invention

As a result of intensive studies, the present inventors have found that such a peculiar graying phenomenon in detergent particles containing a crystalline alkali metal silicate and a nonionic surfactant is caused by the crystalline Al-Li Due to the small difference between the refractive indices of the metal and nonionic surfactants, and especially the effect of incorporation of iron in the process up to the powder preparation of crystalline alkali metal silicate Is bigger.

The present inventors have found that, due to the small difference in the refractive index between the crystalline alkali metal silicate and the nonionic surfactant, the crystalline alkali metal silicate covers the nonionic surfactant. By doing so, it was found that diffuse reflection at the interface was substantially suppressed, and that this was to provide a sense of transparency. Also

Usually, the crystalline alkali metal gaylate is obtained in the form of a block or a sintered product having a size of several cm or more, and is used as a raw material for detergent particles. The step of atomizing during the step of manufacturing the pulp is inevitable as described above. This added atomization step enables the atomization (pulverization) of the crystalline alkali metal silicate in addition to the iron content in the firing raw materials (water glass raw material, alkaline sources such as NaOH, etc.). As a result, iron is mixed in, and such a small amount of the contaminant causes a great effect on the hue of the detergent particles. The same applies to conventionally used builders (zeolite, carbonate, etc.). Although there is a possibility of coloring due to the same principle, the crystalline alkali metal silicate is harder than the builder, so that more iron is contaminated during the pulverization process and the nonionic interface Since the difference in the refractive index between the surfactant and the surfactant became smaller, the combined use of the crystalline alkali metal silicate and the nonionic surfactant resulted in a specific graying phenomenon.

On the other hand, Honkisha and others chose raw materials with the least amount of Fe mixed, and in the process of manufacturing detergent particles by using a crystalline Al-Kyri-Kai-Gayate, which was devised a powdering method. The present inventors have found that the above object can be achieved by remarkably suppressing the mixing of iron, and have completed the present invention. That is, the gist of the present invention is:

(1) detergent particles containing at least 10% by weight of a nonionic surfactant and at least 1% by weight of a crystalline alkali metal silicate having an average particle diameter of 1 to 60 zm; The compounding weight ratio of the ionic surfactant to the crystalline alkali metal silicate is 20 to 1 to 20 and the iron content in the crystalline alkali metal silicate is F Detergent particles characterized as having an e of 14 O ppm or less.

(2) The detergent particles according to the above (1), wherein the nonionic surfactant is a polyoxyethylene alkyl ether.

(3) The above (1) or (2), wherein the crystalline alkali metal silicate is Si 02 / t 0 (where M is an alkali metal) = 0.9 to 2.6. 2) the detergent particles described,

(4) The detergent particles according to any of (1) to (3) above, wherein the crystalline alkali metal gaylate has a composition represented by the following formula (I):

XM ₂ 0yS i 02z M e „0» wH ₂ 0 (I)

(Where M is an element of group Ia of the periodic table, Me is IIa, Hb, Ili a, One or a combination of two or more elements selected from group IVa or VI11, yZx ^ O.9 to 2.6, z / x = 0.01 to 1.0, n / m = 0 .5 to 2.0, w = 0 to 20. )

(5) The detergent particles according to any one of the above (1) to (3), wherein the crystalline alkali metal gaylate has a composition represented by the following formula (II):

_{M 2 0 · x 'S i} 0 2 · y' H 2 0 (II)

(In the formula, M represents an aluminum alloy, and X ′ = S〜2.6.y ′ = 0 020.)

(6) Any one of the above items (1) to (5), wherein the surface of the particles composed of the crystalline alkali metal silicate is covered with a nonionic surfactant in a continuous phase. Described detergent particles,

(7) The detergent particles according to any one of (1) to (6), wherein the L value is 90% or more; and

(8) A granular detergent composition comprising the detergent particles according to any one of (1) to (7). BEST MODE FOR CARRYING OUT THE INVENTION

In the detergent particles of the present invention, in a detergent particle system in which a crystalline alkali metal silicate and a nonionic surfactant are used in combination, iron contained in the crystalline alkali metal silicate is defined as Fe. It is characterized in that the amount is 14 Oppm or less. In the present invention, the amount of iron contained in the crystalline alkali metal silicate is preferably less than or equal to 120 Oppm as Fe, and more preferably less than or equal to 100 ppm.

As described above, by reducing the iron content in the crystalline alkali metal silicate to 140 epm or less as Fe, detergent particles having good whiteness can be obtained. Here, the iron content is determined by completely assimilating 0.5 g of the detergent sample, dissolving it in 2 ml of 6N HC1, diluting it, and analyzing it (ICP; plasma emission analysis). Is measured by The L value measured with a Nippon Denshoku colorimeter 1001 DP type was used as an index of whiteness. In the present invention, the L value is preferably 90% or more.

In order to reduce the iron content to 140 ppm or less as Fe, in addition to selecting a raw material with a small amount of F p mixed halo, X It is necessary to prevent iron from being mixed in the pulverization (pulverization) process. For example, in principle, a method using a device S for pulverizing mainly by contact between massive particles (mass), a method of changing the material of a member used for pulverization of a powdering device, and the like are used.

More specifically, as a method of using a device that powders by contacting powders in principle mainly, as in the case of a vertical roller-mill as a powdering device, mainly a method of contacting agglomerate particles is used. By using the powdered form, it is possible to reduce the amount of iron mixed in as compared with the powdered form obtained by contact between the powder and the body of iron such as a hammer mill. Examples of such a pulverizing apparatus include a vertical roller mill, a roll mill, and a counter target minole (a device that causes particles in a lump to collide).

In addition, as a method of changing the material of a member to be powdered, a device containing iron, such as a hammer mill, is used for powdering massive particles due to contact between powder and iron of the main body. instead of cemented carbide quality alloys, or using a material such as sera mission-box, by spraying method or a lining method, the member surface Unaryo this _t include a method of or coated with the material used in industry As a powdering device with excellent powdering ability, in addition to a hammer mill, a jet minole (colliding with a collision plate) And the like.

In addition, a method of mildly adjusting powdering conditions by, for example, reducing the hammer rotation speed of a hammer mill, reducing the vibration frequency of a vibrating mill, or reducing the rotation speed of a ball mill is known as Fe. This is considered to prevent the contamination of the crystalline alkali glycolate, but it is practically unfavorable on an industrial level because the processing speed is reduced.

In addition, it is necessary to prevent the incorporation of iron components during transportation in the manufacturing equipment. For example, by the commonly used pneumatic transportation, detergent particles collide with the inner wall of the iron pipe (particularly from the arm (curved pipe)). ) Iron easily mixes. In order to prevent this, the inner wall of the iron pipe may be covered with alumina ceramic or the like, or rubber lining, resin pipe, etc. may be used. The mixing of metals such as niggels and chromium contained in the powdered member of the present invention is also reduced at the same time, whereby the hue can be improved.

The cleaning particles of the present invention contain at least 10% by weight of nonionic surfactant, especially at least 15% by weight, more specifically at least 20% by weight, and at least 1% by weight of crystalline alkali metal gaylate, 3% by weight or more, more specifically 5% by weight or more, and the mixing ratio of both components is such that the ratio of nonionic surfactant / crystalline alkali metal / gamma acid salt = 20 Ζ 1-1 to 20, especially 20 / l to lZ5, etc. are also used effectively in detergent particles which are also clearly 0/1 to 13 and the iron content is within the above range. Except for this, the manufacturing method, components other than iron, and the composition thereof are the same as those of generally known detergent particles, and are not particularly limited.

Examples of the nonionic surfactant include the following.

That is, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene sorbitan fat Acid ester, boroethylene ethylene sorbite fatty acid ester, polyethylene glycol fatty acid ester, borooxyethylene glycol fatty acid alkyl ester, polyoxyethylene borooxypropylene alkyl ether, polyoxyethylene castor oil, polyoxyethylene Arukiruami down, glycerin fatty acid esters, high pole fatty Al force Norua Mi de, alkyl glucosides and passes, alkyl glucose § Mi _de,-to Arukirua Mi emissions be described de, and the竽down

Among these nonionic surfactants, it is preferable to use polyoxyethylene alkyl ether from the viewpoint of cleaning performance and the like.

More preferably, an alcohol of 10 to 18 is added with an average of 5 to 15 moles of ethylene oxide, and an alcohol of an average of 12 to 14 carbons is added with an average of 6 to 10 moles of ethylene oxide. Things are even better.

Crystalline Alkali Lithium Casilicate

The crystalline alkali metal gaylate used in the present invention has not only an alkali ability but also an ion exchange ability, and can further reduce the standard usage amount of the detergent composition.

Further, the powdered crystalline alkali metal gaylate used in the present invention preferably has an average particle diameter of 1 to 60 m, more preferably an average particle diameter of 1 to 30 m. . If the average particle size exceeds 60 m, the ion exchange rate tends to be slow, causing a reduction in the cleaning performance, and also causing adhesion and remaining on clothes after cleaning.

The average particle size and particle size distribution are measured using a laser diffraction type particle size distribution analyzer. That is, about 200 ml of ethanol was injected into the measuring cell of the laser diffraction particle size distribution analyzer SLA-700 type (manufactured by HORIBA, Ltd.), and about 0.5 to 5 mg of the sample was placed in ethanol. During ~ Suspend. Subsequently, the sample was stirred for 1 minute while irradiating with ultrasonic waves to sufficiently disperse the sample. Then, a He-Ne laser (632.8 nm) was injected 0, and the diffraction and scattering pattern was used. Measure the particle size distribution. The analysis uses both Fraunhofer diffraction theory and Mie scattering theory, and measures the particle size distribution of suspended particles in the liquid in the range of 0.04 to 262 m. The average particle size is the median size of the particle size distribution.

Such an average particle diameter can be achieved by adjusting a powdering method and powdering conditions.

As the crystalline alkali metal gaterate used in the present invention, S i 0 ₂ / t 0 (where M is an alkali metal) of the alkali metal gaylate is 0.9 to 2.6. Those are preferred, more preferably 1.5 to 2.2. If the alkali metal gaylate S i O s ZMz O is less than 0.9, the water resistance is insufficient and caking deterioration is liable to occur, and if the S i 02 / M ₂₀ exceeds 2.6, the alkali ability and ion Exchangeability is also reduced, and cleaning performance is likely to deteriorate.

Among the crystalline alkali metal gaterates used in the present invention, preferred are those having the following compositions (I) and (II).

① xM ₂₀ · y S i 02 · z M e »0„ · wH ₂ 0 (I)

(In the formula, M represents an element of Group Ia of the periodic table, Me represents one or a combination of two or more elements selected from Ha, lib, I [Ia, IVa, or VIH elements. xO.9 to 2.6, z / X = 0.01 to 1.0, n / m = 0.5 to 2.0, w = 0 to 20.)

② M ₂₀ · x 'S i 0 ₂ · y' H ₂₀ (II)

(In the formula, M represents an alkali metal, X ′ = 1.5 to 2.6, and y ′ = 0 to 20.)

First, the details of the crystalline alkali metal silicate of the above composition ① Will be described.

In the general formula (I), M is selected from Group Ia elements of the periodic table, and examples of Group Ia elements include Na and K. They have a alone may constitute a may have a mixture of two or more, for example, N a ₂ 0 and K ₂ 0 Toga混combined and Micromax ₂ 0 component.

Me is selected from IIa.Ilb, [I [a, IVa or VII [group element of the periodic table, and {{Mg, Ca, Zn, Y, Ti, Zr, Etc. can be enjoyed. These are not particularly limited, but are preferably Mg and Ca from the viewpoint of resource and safety. These may be used alone or as a mixture of two or more kinds. For example, MgO, CaO and the like may be mixed to constitute the Me „0» component.

The crystalline alkali metal silicate of the present invention may be a hydrate. In this case, the hydration amount is in the range of w = 0 to 20.

In the single-split type (I), / is 0.9 to 2.6, preferably 1.5 to 2.2. When y / x is less than 0.9, the obtained crystalline alkali metal silicate has insufficient water resistance, and significantly affects the powder properties of the detergent composition such as caking property and solubility. If yZx exceeds 2.6, the resulting alkali metal silicate of the alkali metal has a low ability to reduce the strength and becomes insufficient as a reducing agent, and also has a low ion exchange capacity, and can be used as an ion exchanger. Not enough. τ / X is from 0.01 to 1.0, preferably from 0.02 to 0.9. When Ζχ is less than 0.01, the obtained crystalline alkali metal gayate has insufficient water resistance, and when it exceeds 1.0, the ion exchange capacity of the crystalline alkali metal gayate obtained is not sufficient. And is insufficient as an ion exchanger. X, y, z are shown in yZx and z Zx above. The relationship is not particularly limited as long as the relationship is as follows. When xM ₂₀ is, for example, x ′ N aa 0 · X ″ K _{20 as} described above, X is χ ′ + X ″. Such relationships, ZME "O _n component is. Or the same in the z in a case consisting of more than two, NZM = 0. 5 to 2. 0 is coordinated oxygen ions to the element _U , which is effectively selected from the values of 0.5, 1.0, 1.5, and 2.0

Crystalline alkali metal厲Kei salt in the present invention is made from three components of _{_{M 2 0, S i 0 2}} , M e m 0 " as shown in the general formula (I) above. Thus, the present In order to produce the crystalline alkali metal gaterate of the present invention, a material that can be converted into each component is required as a raw material, and in the present invention, a known compound is appropriately used without any particular limitation. . for example, M ₂ 0 component, the Me »O n component, alone or oxides of the composite of each of the elements, hydroxides, salts, and the element-containing minerals is used. Specifically, for example, M ₂ 0 the components of the raw material, N a OH, KOH, as _{_{N a 2 C 0 3, K}} 2 C 0 3, N a 2 S 04. etc. Me. 0 »component of the raw materials, C a C 0 _3, M g C 03. and _{C a (OH) 2, M} g (OH) 2, M g 0, Z r 0 2 Doromai preparative like. S i 0 ₂ component ο the Ke I stone, kaolin, talc, fused silica, silicate source one da, etc. are used

In the method for preparing the crystalline alkali metal gaylate of the present invention, the above-mentioned raw material components are mixed at a predetermined quantitative ratio so that the desired values of X, y and z of the crystalline alkali metal gaylate are obtained. However, there is exemplified a method of crystallization by firing in a range of usually 300 to 150, preferably 500 to 100'C, and more preferably 600 to 900 '. You. In this case, When the heat temperature is lower than 300 ° C., the crystallization is insufficient, and the obtained crystalline alkali metal silicate is poor in water resistance, and it is 1500. If it exceeds C, it becomes coarse particles and the ion exchange capacity decreases. The heating time is usually 0.1 to 24 hours. Such firing can be usually performed in a heating furnace such as an air furnace or a gas furnace.

Next, a detailed description will be given of the crystalline alkali metal silicate having the above-mentioned composition (2).

This crystalline alkali metal gaylate has the general formula (II):

Μ ₂₀・ χ 'S i 0 ₂ -y' H ₂ 0 (II)

It is represented by

Among these, those in which x 'and y' in the general formula (II) are 1.7 ≤ χ '≤ 2.2 and' = 0 are preferable, and the cation exchange capacity is at least 100 C a C 03 mg / g or more, preferably 200 to 400 CaCO3 mg, and the crystalline alkali metal silicate is one of the substances having an ion scavenging ability in the present invention. is there.

Such a crystalline alkali metal gaylate is described in Japanese Patent Application Laid-Open No. 60-227,895, and its production method is generally described as follows. It is obtained by baking at 1000 to make it crystalline. Details of the synthesis method are described in, for example, Phys. Chem. Glasses. 7, 127-138 (1966), Z. Kristallogr., 129. 396-404 (1969). Further, as the crystalline alkali metal Gay salt tradename than Tatoebaeki be sampled Inc. "Na-SKS-6" _{_{_{(6 -Na 2 Si 2 0 5}}} ), powdered, those granular available .

The cleaning particles of the present invention comprise a nonionic surfactant and a crystalline aluminum alloy. It contains a maleic acid salt as an essential component. Other components include surfactants other than nonionic surfactants described later, amorphous alkali metal silicates, and alkali metal gays. Non-acid salt metal ion sequestering agent, alkali agent, non-dissociated polymer, organic acid salt builder, anti-fading agent, anti-staining agent, anti-caking agent, anti-oxidant, anti-foaming agent, bleaching agent, It may contain a bleaching activator, a fluorescent dye, a bluing agent, a fragrance and the like.

When the nonionic surfactant accounts for 50% by weight or more of all the surfactants in the detergent particles, the effect of the present invention is more remarkably exhibited. However, the production method is not particularly limited, and a conventionally known method can be used. For example, a granulation method described in JP-A-5-209200, JP-A-3-16001 and JP-T-6-520445 may be mentioned. . It is preferable that the crystalline alkali metal gaterate is dry-dried during granulation of the detergent particles of the present invention, and when spray-dried particles are used, a nonionic surfactant is blended in the slurry composition. Alternatively, a nonionic surfactant may be directly added to the crystalline alkali metal gaterate by dry driving, and a continuous phase is coated on the surface of the crystalline alkali metal gaterate. In the state, the effect of the present invention is particularly remarkable.

The average particle diameter of the detergent particles obtained by the above production method is preferably from 200 to 800 m, and particularly preferably from 300 to 600/111. The density of JIS K 336 2 is preferably at least 600 g / L, particularly preferably from 700 to 1 OO gZL.

A granular detergent composition comprising the detergent particles of the present invention Except for the fact that the content of iron in detergent particles *, the content of nonionic surfactant, and the content of crystalline alkali metal silicate are within the above ranges, The components and the composition of are generally the same as those of known granular detergent compositions, and are not particularly limited.

For example, based on the detergent particles, at least one or more enzymes, a bleaching agent, a bleaching activator, and various types of particles each containing Z or an antifoaming agent as a main component may be dried to obtain granularity. Washing may be carried out, or a conventional detergent having an anionic surfactant as a main base may be used in such a manner that the various particles are after-blended as builder particles. In any case, it is needless to say that the aesthetic appearance of the entire detergent becomes suitable. Hereinafter, other components will be described in detail with respect to the entire composition containing the detergent particles. Surfactants other than Nonionic surfactant

Surfactants other than the nonionic surfactant used in the present invention are not particularly limited, and those which can be generally used for detergents can be used. As the surfactant other than the nonionic surfactant, specifically, at least one selected from the group consisting of an anionic surfactant, a cationic surfactant and an amphoteric surfactant exemplified below. It is.

Examples of anionic surfactants include alkyl benzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, α-sulfuric acid sulfonates, hysulfo fatty acid salts and α-sulfo fatty acid esters. Examples thereof include salts, alkyl or alkenyl ether carboxylate, amino acid type surfactants, Ν-amino acid type surfactants, and the like. Acid sulfate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate and the like.

Examples of the cationic surfactant include a quaternary ammonium salt such as an alkyltrimethylamine salt. Examples of the amphoteric surfactant include an amphoteric surfactant such as a sulfoxy type or a sulfobetaine type.

The content of the surfactant, S, is preferably 1 -'- 45% by weight in the total grain washing composition. Crystalline Al Force. Sequestering Agents Other than Lithium Casilicate.

The metal ion sequestering agent other than the crystalline alkali metal salt of the present invention preferably has a Ca ion trapping ability of 200 Ca C 03 mg Zg or more.

In particular, those containing 10% by weight or more of a carboxylate polymer are preferable. Specific examples of such a polymer include a polymer or a copolymer having a repeating unit represented by the general formula (II). Be mentioned

X 1 2

I I

—— C H —— C ——

C 00 χ ₃

(Wherein X, is methyl, Η or COOX ₃ , X ₂ is methyl, Η or 、, Χ ₃ is Η, an alkali metal, an alkaline earth metal, ΝΗ

Indicates 4 or ethanolamine. )

In the general formula (III), examples of the alkali metal include Na, K, and Li, and examples of the alkaline earth metal include Ca and Mg. It is.

The polymer or copolymer used in the present invention includes, for example, acrylic acid, (anhydrous) maleic acid, methacrylic acid, -hydroxyacrylic acid, crotonic acid, isocrotonic acid, and It is synthesized by a polymerization reaction of its salt or the like, a copolymerization reaction of each monomer, or a copolymerization reaction with another polymerizable monomer. Examples of other copolymerized monomers used for the copolymerization at this time include, for example, aconitic acid, itaconic acid, citraconic acid, fumaric acid, vinylphosphonic acid, and sulfonated maleic acid. , Diisobutylene, styrene, methyl vinyl ether, ethylene, propylene, isobutylene, pentene, butadiene, isoprene, vinyl acetate (and vinyl alcohol if hydrolyzed after copolymerization), acrylic acid ester, etc. However, there is no particular limitation. The polymerization reaction is not particularly limited, and a generally known method can be used.

In addition, a polymer of a polyboretal carboxylic acid such as polyglyoxylic acid described in Japanese Patent Application Laid-Open No. 54-512196 can also be used.

In the present invention, as the above-mentioned polymer and copolymer, those having a weight average molecular weight of 800 to 100,000 are used, and preferably those having a weight average molecular weight of 500,000 to 200,000 are used. .

In addition, the copolymerization ratio of the repeating unit of the general formula (Ι Π) with another copolymer monomer in the case of copolymerization is not particularly limited, but is preferably a copolymer of the general formula (111). Polymerization monomer = copolymerization ratio in the range of 1/100 to 90/10.

In the present invention, the above-mentioned polymer or copolymer is preferably blended in an amount of 1 to 50% by weight, more preferably 2 to 30% by weight, and particularly preferably 5 to 15% by weight in the total composition. Further, an aluminoate having an ion exchange capacity represented by the following formula (IV) of 200 mg / g or more can be used.

_{X "(Μ 2 0) ·} A1 2 0 3 - y" (Si0 2) - w "(H 2 0) (IV)

(Where M is an alkali metal such as sodium and potassium, and X ", y", and w "represent the number of moles of each component. Generally, 0.7 ≤ X" ≤ 1.5, 0.8 ≤ y "≤ 6, w" is 0 to 20.)

Examples of the above-mentioned aluminosilicates include crystalline ones and non-β Φ ones, and particularly preferred are those represented by the following general formula.

N a 2 0A 1 ₂ 0 aY y S i 02W H ₂ 0

(In the formula, y represents a number of 1.8 to 3.0, and w represents a number of 1 to 6.)

As the crystalline aluminosilicate (zeolite), synthetic zeolite having an average primary particle diameter of 0.1 to 10 m typified by A-type, X-type, and P-type zeolite is preferably used. Zeolite may be used as powder and Z or zeolite slurry or zeolite aggregated and dried particles obtained by drying the slurry.

The above crystalline aluminosilicate can be produced by a conventional method. For example, the methods described in JP-A-50-12881 and JP-A-51-28505 can be used.

On the other hand, the amorphous aluminosilicate represented by the one-branch method similar to the above-mentioned crystalline aluminosilicate can be produced by an ordinary method. For example, S i 0 (where M means alkali metal) ₂ and M ₂ O is _{S i 02 / M 2 0 =} 1. 0~4. 0 molar ratio is, H ₂ 0 and M ₂ 0 molar ratio with silicate al force Li metal salt aqueous solution is _{_{H 2 OZM 2 O = 1 2~2}} 0 0 of which the M ₂ 0 and a molar ratio of l ₂ 03 is M ₂ 0 / a 1 ₂ 03 = 1.0 to 2. 0, the molar ratio of H ₂ 0 and M ₂ 0 is H ₂ 0 / In M ₂ 0 = 6. 0~ 5 Normal 1 5-6 0 Low alk Riarumi phosphate alkali metal salt solution that is a 0 0, preferably 3 0 to 5 O ^e also DOO in strong the temperature of the C擾拌Add below. At this time, the addition method may be a method of adding an aqueous solution of an alkali metal silicate to an aqueous solution of a low alkali alkali metal aluminate.

The resulting white sediment slurries are then subjected to a temperature of usually 70 to 100, preferably at a temperature of 30 to 100C, usually for more than 10 minutes and less than i0B 閗, preferably for 5 hours. It can be advantageously obtained by performing a heat treatment, followed by filtration, washing and drying.

By this method, an amorphous aluminosilicate oil-absorbing carrier having an ion exchange capacity of 100 CaCO ₃ mgZg or more and an oil absorption capacity of 80 m1 / 10 Og or more can be easily obtained. (See Japanese Unexamined Patent Publication No. Sho 62-191,417 and Japanese Unexamined Patent Publication No. Sho 62-191,199)

Other metal ion sequestering agents include aminotriethylene (methylenephosphonic acid), 1-hydroxyxethylidene 1,1-diphosphonic acid, ethylenediamine tetra (methylenephosphonic acid), and diethylenetriamine. (Methylene phosphonic acid) and their salts; salts of phosphonocarboxylic acids such as 2-phosphonobutane-1- and 2-dicarboxylic acids; salts of amino acids such as aspartic acid and glutamic acid , Trinitrate salts, aminoboroacetates such as ethylenediaminetetranate, etc. 0

Other components in the present invention include, as alkali agents, crystalline and amorphous alkali metal silicates, and alkali metal salts such as carbonates and sulfites and organic amines such as alkanolamines. And various kinds of compounds.

In addition, polyethylene glycol, polyvinyl alcohol, polypropylene Non-dissociating polymers such as nilpyrrolidone; builders such as salts of organic acids such as diglycolic acid and oxycarbonate; carboxymethylcellulose; anti-fading agents that are generally known to be incorporated into detergents; recontamination And an inhibitor.

In addition, the following components can be contained. That is, enzymes such as protease, lipase, cellulase, and amylase, lower alkylbenzene sulfonates having about 1 to 4 carbon atoms, fu, rufosuccinate, sulk, calcium silicate, etc. An anti-caking agent, an antioxidant such as tert-butylhydroxytoluene and distyrenated cresol, a bleaching agent such as sodium percarbonate, or a bleaching activator such as tetracetylethylenediamine; It may contain a fluorescent dye, a bluing agent, a fragrance, etc., but these are not particularly limited, and may be blended according to the purpose.

Hereinafter, the present invention will be described in more detail with reference to Preparation Examples, Examples, and Comparative Examples, but the present invention is not limited to these Examples and the like. Preparation Example 1

Crystalline Alkali Lithium metal silicates are available in several lots in powdered Na-SKS-6 (Hexst, average particle size 120 zm, Fe content 90 ppm). Among them, those having a relatively low Fe content were used and pulverized under the following conditions to obtain pulverized crystalline alkali metal gaterates A to C. Crystalline Al force

Ishikawajima-Harima Heavy Industries, Ltd. “IS-150” Vertical Roller Mill Under the following conditions, the powdery Na—SKS-6 was pulverized to obtain a pulverized crystalline alkali metal gaterate A.

Table rotation speed: 30 rpm,

Cylinder hydraulic pressure for lowering roller: ZO k gZ cm ² ,

Severe overnight rotation speed: 150 rpm,

Air flow: 8 m ³ Z minutes,

Processing amount: 30 kg.Zh

The average particle size of the crystalline metal silicate pulverized product A was 25 m, and the amount of Fe mixed into the pulverized product was 104 ppm. Crystalline Al force

Powdered Na-SKS using Hosokawa Miclon Co., Ltd. “ACM-10” ACM pulverizer (all powder-welded parts are made of ceramics (PSZ)) under the following conditions. -6 was pulverized to obtain a crystallized alkaline metal silicate powder B.

Rotor speed: 5400 rpm,

Separation evening rotation speed: 1500 rpm,

Air volume: 1 ³ m 3 Z minutes,

Processing amount: 200 k gZh

The average particle size of the crystallized alkaline metal silicate pulverized material B was 29 β τη ^, and the amount of Fe mixed into the pulverized material was 90 ppm. Crystalline Al Force

The pulverization was performed under the same conditions as for the above-mentioned pulverized material B, using a powdered part of the ACM pulverizer made of SUS steel SUS304. The average particle size is 28 m, and the amount of Fe Preparation Example 2 (Amorphous aluminosilicate)

Sodium carbonate was dissolved in ion-exchanged water to prepare a 6% by weight aqueous solution. A solution of 132 g of this aqueous solution and an aqueous solution of sodium aluminate (Cone. 50 weight 38.28 g) was placed in a 100 ml-capacity reaction vessel with a baffle plate, and the resulting mixed solution was strongly applied. Under stirring, 21.4 g of No. 3 water glass diluted with twice the amount of water was allowed to react while dripping over 40 minutes at 40. In this case, blowing CO ₂ gas was performed. The pH of the reaction system was controlled (pH = 10.5) to optimize the reaction rate, and then the reaction system was heated to 50 and stirred at the same temperature for 30 minutes. blown with C 0 ₂ gas into the reaction system to neutralize the excess alkali

(pH = 9.0). The obtained neutralized slurry was filtered under reduced pressure using a furnace paper (No. 5C, manufactured by Toyo Shoji Co., Ltd.). Relying cake, 1 0 0

The plate was washed with water 0 times and dried by drying (at 105, 300 torr, 10 hours). Further, crushing was performed to obtain an amorphous aluminosilicate powder of the present invention. The aqueous solution of Tuda aluminate was placed in a 100 cc four-necked flask with Al (OH) 32 43 g and a 48% by weight NaOH aqueous solution 2.

98.7 g was added and mixed, heated to 110 with stirring, and dissolved for 30 minutes to prepare.

The composition of the resulting amorphous aluminosilicate, atomic absorption analysis and bra Zuma emission spectroscopy folding _{_{results, A l 2 0 3 = 2}} 9. 6 wt%, S i 02 = 5 2. 4 wt%, N a ₂ 0 = 1 8. was 0 _{wt% (1 0 N a 2 0} · a 1 2 0 3 -. 3. 1 0 S i O 2). The amorphous aluminosilicate had the following characteristics. C a ion trapping capacity is 18.5 C a C 0 ₃ mgZg, oil absorption capacity is 28.5 ml Zl 0 g, pore size less than 0.1 m The ratio of the pore volume with a pore diameter of 9.4%, 0.1 zm or more and 2.O xm or less is 76.3%, and the water content is 11.2. % By weight. Examples 1-2

Put 2.5 kg of the obtained pulverized material A and 0.75 kg of amorphous aluminosilicate in a digue mixer, and carry the polyoxyethylene alkyl ether (C, ₂ , E0 = 6) at room temperature while carrying. Agitation tumbling granulation was performed while gradually dropping 1.25 kg. After the granulation step, 0.5 kg of 4A zeolite powder was added, and the obtained particles were subjected to surface modification to obtain detergent particles.

Detergent particles were obtained through the same operations and steps as described above, using the crushed crystalline aluminum metal salt B instead of the crushed material A. Comparative Example 1

Detergent particles were obtained through the same operations and steps as described above, using the crystalline aluminum carbonate powder C instead of the above powder A. Table 1 shows the Fe content, whiteness, and hue evaluation results of the detergent particles obtained in the above Examples and Comparative Examples.

The iron content was measured by completely ashing 0.5 g of detergent particles, dissolving them in 2 ml of 6N HC1, diluting and analyzing (ICP; plasma emission analysis). The L value measured with a Nippon Denshoku colorimeter 1001 DP was used as an index of whiteness. Example Comparative example

Detergent particle composition

(Weight 1 2 1

A 50

Crystalline rukari metal silicate B 50

r 50

Polyethylene alkyl ether (C i ₂ E0 ₈ ) 25 25 25

Amorphous silicon silicate 15 15 15

4 A zeolite powder 10 1 0 10

Fe content in detergent particles (ppm) 57 50 85

Detergent particle whiteness (L value) 90 93 76

Detergent particle hue visual evaluation: 2 × * ³ White.

Almost white

It was gray.

Industrial applicability

The detergent particle of the present invention is a detergent particle containing a crystalline alkali metal silicate having excellent sebum cleaning performance and a nonionic surfactant, and has an improved hue and a good whiteness. It has high commercial value. Therefore, the granular detergent composition of the present invention containing such detergent particles also has good whiteness.

In the present invention described above, there are various types in the range of obvious identity. Such variations are not considered to depart from the spirit and scope of the invention, and all such modifications that are obvious to those skilled in the art are included within the scope of the following claims.

- twenty three -

Claims

The scope of the claims

1. The amount of the nonionic surfactant is 10% by weight or more,

1% by weight or more of crystalline alkali metal gaterate having an average particle size of 1 to 60 m

Wherein the weight ratio of the nonionic surfactant to the crystalline alkali metal silicate relative to the crystalline alkali metal salt is 210-1 to 20%; Detergent particles characterized in that the iron content in the lithium silicate is 14 O ppm or less as Fe.

2. The detergent particles according to claim 1, wherein the nonionic surfactant is a borioquineethylene alkyl ether.

3. The crystalline alkali metal厲Kei salt is S i 0 ₂ / Ut 0 (wherein, M is alkali metal) according to claim 1 or 2, characterized in that = the 0.9 to 2.6 The detergent particles as described.

4. The detergent particles according to any one of claims 1 to 3, wherein the crystalline alkali metal silicate has a composition represented by the following formula (I).

XM ₂ 0yS i 02-z M e »0„ wH ₂ 0 (I)

(In the formula, M represents an element of Group Ia of the periodic table, Me represents one or a combination of two or more elements selected from IIa, IIb, Ilia.IVa or VIII elements, and yZx = 0. 9 to 2.6, z / X = 0.01 to 1.0, n / m = 0.5 to 2.0, w = 0 to 20.)

5. The crystalline alkali metal silicate is represented by the following formula (II). The detergent particles according to any one of claims 1 to 3, wherein the detergent particles have a composition.

Μ ₂₀・ · 'S i 0 ₂ -y' H ₂ 0 (II)

(In the formula, M represents an alkali metal, x ′ = 1.5 to 2.6, y * = 0 to 20.)

6. The method according to any one of claims 1 to 5, wherein the surface of the particles formed of the crystalline metal salt of lithium metal is coated with a non-ionic surfactant and a surfactant in a continuous manner. The detergent particles as described in any one of the above.

7. The detergent particles according to any one of claims 1 to 6, wherein the L value is 90% or more.

8. A granular detergent composition comprising the detergent particles according to any one of claims 1 to 7.